CN106876741A - A kind of preparation method of compoiste proton exchange film - Google Patents
A kind of preparation method of compoiste proton exchange film Download PDFInfo
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- CN106876741A CN106876741A CN201510919483.XA CN201510919483A CN106876741A CN 106876741 A CN106876741 A CN 106876741A CN 201510919483 A CN201510919483 A CN 201510919483A CN 106876741 A CN106876741 A CN 106876741A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The present invention relates to Proton Exchange Membrane Fuel Cells field, the preparation method of a kind of low cost and the compoiste proton exchange film of high stability is disclosed.It is characterized in that preparing sulfonated polyether-ether-ketone film and as basement membrane first with solution casting method, plasma spray technology is recycled, prepare the composite membranes layer by layer of the NF/SPEEK containing transition zone.Battery testing shows that the composite membrane peak power has been higher by 40% or so than commercialization NR212 films.The film not only inherits the high-performance of pure SPEEK films, while comparing pure SPEEK films, its durability improves 5-6 times.
Description
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells technical field, a kind of inexpensive and high stability is specifically related to
The preparation method of compoiste proton exchange film.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of energy converting means that chemical energy can be converted into electric energy
Put.Its operation principle is similar to internal combustion engine, as long as constantly giving its base feed, with regard to output electric energy that can be lasting.PEMFC has
Have the advantages that energy conversion efficiency (40-60%) higher, environmentally friendly, toggle speed be fast, long working life, therefore
By more and more extensive concern, particularly it is in the wide application of the aspects such as automobile power, portable power source and small hydropower station
Prospect.But in fact, the stability and durability of fuel cell are always to hinder its technological progress, commercialized thorny difficulty of marching toward
Topic.This problem is especially serious for PEM.Current commercialized PEM is du pont company's production
'sSerial perfluoro sulfonic acid membrane, butFilm price is high, and its cost account for whole fuel cell pile
50%.Therefore the cheap and PEM with superior performance is developed, is always the emphasis and focus of membrane material research.Sulfonation
Polyetheretherketonepolymer polymer is because of sulfonation degree controllable, and polarization performance is close to even better thanSeries membranes and enjoy pass
Note.
The content of the invention
It is an object of the invention to provide a kind of low cost and the preparation method of the compoiste proton exchange film of high stability.
The composite membrane includes sulfonated polyether-ether-ketone basement membrane (A), perfluorinated sulfonic acid polymer layer (C) and intermediate layer (B).The method with
Cheap sulfonated polyether-ether-ketone material makees basement membrane, by thermal spraying ancillary technique, stability perfluor higher is imposed on basement membrane
Transition composition of layer in the middle of sulfonic acid polymer layer, basement membrane and perfluorinated ionomer layer is sulfonated polyether-ether-ketone and perfluorosulfonate ionomer
Mixture.
Sulfonated polyether-ether-ketone and perfluorinated sulfonic acid polymer all contain sulfonic group, and the two can have one preferably by sulfonic group
With reference to.Therefore the presence of intermediate layer, can slow down the incompatibility between two kinds of polymer material.Prepared using the method
Composite membrane, greatly reduces the cost of PEM, and the hydrogenation electric current of composite membrane is low, and monocell performance is higher than
Nafion212 films, the monocell stability under certain current density has larger lifting compared to pure SPEEK.
Technical scheme is as follows：
The preparation method of a kind of low cost and the compoiste proton exchange film of high stability, comprises the following steps：
1. by the sulfonated polyether-ether-ketone resin that sulfonation degree is 0.54~0.82, it is dissolved in aprotic solvent, casting film is obtained
Liquid, and in an oven in casting film is cast on glass plate, casting solution concentration is preferably 5%~15%, and the aprotic solvent of casting film is excellent
Elect as among N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc) and the pyrrolidones of N- methyl -2 (NMP)
One kind, oven temperature is 70~120 DEG C, and process time is 6~24h.
2. the sulfonated polyether-ether-ketone by above-mentioned preparation makees basement membrane, is fixed on thermal spraying operating desk, using spray gun in basement membrane
Transition zone and perfluorinated sulfonic acid polymer layer on surface spraying, perfluorinated sulfonic acid polymer resin is one kind of side chain long or short-side chain,
Resin solution concentration is 3%~15%, and the content ratio (mass ratio) of two kinds of polymer resin is in transition zone, sulfonated polyether ether
Ketone：Perfluorinated sulfonic acid polymer=1:0.6~1:1.2, the operating desk temperature of thermal spraying is set in 40 DEG C~80 DEG C
3. after transition zone in thermal spraying, need to continue to spray perfluorosulfonate ionomer solution, spraying conditions with step 2, most
The composite membrane that will have been sprayed afterwards is placed in baking oven and processes, and oven temperature is 70~120 DEG C, and process time is 6~24h.In addition,
In spraying process, the thickness of control transition zone and perfluorinated sulfonic acid layer is in 5~30um.Compared with prior art, the present invention has such as
Lower advantage：
1. the composite membrane can effectively slow down degraded of the sulfonated polyether-ether-ketone film in cathode side.
2. the presence of transition zone, effectively reduces the incompatible appearance between sulfonated polyether-ether-ketone and perfluorinated sulfonic resin.
3. use plasma spray technology, can conveniently realize the preparation of composite membrane layer by layer, and easily controllable sprayed coating thickness.
4. the composite membrane oozes that hydrogen is small, battery performance is high and stability is substantially improved compared to pure SPEEK films, and this is compound
The cost of film is significantly less than existing Nafion series membranes.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of SPEEK films, the films of Nafion 212 and NF/SPEEK films involved in the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph in the section of NF/SPEEK composite membranes involved in the present invention.
Fig. 3 is several films involved in the present invention, the polarization dependence figure of the voltage after assembled battery and current density and
The graph of a relation of power density and current density.
Fig. 4 is pure SPEEK films involved in the present invention and NF/SPEEK composite membranes, in assembled battery after 1000mA cm-2
Lower voltage changes with time graph of a relation.
Fig. 5 is the hydrogenation electric current figure of NF/SPEEK composite membranes involved in the present invention.
Specific embodiment
The present invention is further described below by way of specific implementation example, but the present invention is not limited only to following reality
Apply example.
Embodiment 1
Sulfonation degree (DS) is taken for 77% sulfonated polyether-ether-ketone resin 2.7g, is dissolved in 44g DMAc, be made into mass fraction
It is 5.78% SPEEK casting solutions；Take again after the 5.5g casting solutions and 4g DMAc fully mix, be placed on glass casting film plate, 80
DEG C vacuum drying 12h, temperature is then risen to 100 DEG C and dries 12h, be cooled to place it is standby to room temperature.By above-mentioned preparation
Pure SPEEK films are fixed on thermal spraying platform, take the 5wt%Nafion solution of the above-mentioned SPEEK casting solutions of 0.5ml and 0.5ml
(D520) 0.3ml even applications, are taken after being thoroughly mixed in SPEEK films surface；Then 0.5mlNafion solution is taken again, is continued
Even application is in above-mentioned film surface；The composite membrane that will most spray backward places 4h in exhausting on 65 DEG C of thermal spraying platform, then at
12h is dried in 90 DEG C of baking ovens, natural cooling is that the composite membrane layer by layer is obtained.
The composite membrane is assembled into monocell to be tested, the polarization curve in single pond can see the peak power of composite membrane
Density is up to 1.4W cm-2, considerably beyond the battery performance (maximum power density of N212 films<0.9W cm-2), and single pond exists
1000mA cm-2Lower voltage is remained to be maintained at 0.63V in 70h, and 5-6 times is improve compared to pure its durability of SPEEK film batteries, is seen
Fig. 2, Fig. 3.The operating condition in single pond is：Anode and cathode Platinum loading is 0.5/0.3mg cm-2, battery temperature is 65 DEG C, and hydrogen-oxygen increases entirely
Wet, flow is respectively 0.1/0.2mL min-1。
Embodiment 2
Sulfonation degree (DS) is taken for 64.2% sulfonated polyether-ether-ketone resin carries out solution casting method masking by embodiment 1.Will be upper
The pure SPEEK films for stating preparation are fixed on thermal spraying platform, take the 5wt%Nafion of the above-mentioned SPEEK casting solutions of 0.5ml and 0.8ml
Solution (D520), takes 0.4ml even applications in SPEEK films surface after being thoroughly mixed；Then 0.5mlNafion solution is taken again,
Continue even application in above-mentioned film surface；The composite membrane that will most spray backward places 4h in exhausting on 65 DEG C of thermal spraying platform,
12h is dried in 90 DEG C of baking ovens, natural cooling is that the composite membrane layer by layer is obtained.The assembling test of film is ibid.
Embodiment 3
Sulfonation degree (DS) is taken for 80.2% sulfonated polyether-ether-ketone resin carries out solution casting method masking by embodiment 1.Will be upper
The pure SPEEK films for stating preparation are fixed on thermal spraying platform, take the 5wt%Nafion of the above-mentioned SPEEK casting solutions of 0.5ml and 0.6ml
Solution (D520), takes 0.4ml even applications in SPEEK films surface after being thoroughly mixed；Then 0.5mlNafion solution is taken again,
Continue even application in above-mentioned film surface；The composite membrane that will most spray backward places 4h in exhausting on 65 DEG C of thermal spraying platform,
12h is dried in 90 DEG C of baking ovens, natural cooling is that the composite membrane layer by layer is obtained.The assembling test of film is ibid.
Claims (10)
1. a kind of preparation method of compoiste proton exchange film, it is characterised in that：Basement membrane is made with sulfonated polyether-ether-ketone (SPEEK) film
(A), perfluorinated sulfonic acid polymer layer (C) in its one or both sides thermal spraying, A layers imposes transition zone (B), transition zone with C interlayers
It is made up of with perfluorinated sulfonic acid polymer sulfonated polyether-ether-ketone；Specific preparation process is as follows：
A) sulfonated polyether-ether-ketone is dissolved with aprotic solvent, and sulfonated polyether-ether-ketone basement membrane (A) is prepared using solution casting method；
B) in sulfonated polyether-ether-ketone membrane surface side or the transition zone of two side thermal spraying one (B)；
C) on the basis of step b), further in transition zone (B) thermal spraying on surface last layer perfluorinated sulfonic acid polymer layer (C)；
D) composite membrane prepared in step c) need in an oven make further heat treatment.
2. the preparation method of the compoiste proton exchange film described in claim 1, it is characterised in that：Selected sulfonated polyether
The sulfonation degree of ether ketone is between 0.54~0.82.
3. according to the preparation method described in claim 1, it is characterised in that：A) aprotic solvent of casting film is selected from N, N- diformazans in
One kind among base formamide (DMF), DMAC N,N' dimethyl acetamide (DMAc) and the pyrrolidones of N- methyl -2 (NMP) or two kinds with
On.
4. according to the preparation method described in claim 1, it is characterised in that：The thickness control of basement membrane (A) is in 10~70um.
5. according to the preparation method described in claim 1, it is characterised in that：The perfluorinated sulfonic acid polymer is side chain long or short-side chain
One kind, skeleton symbol：
K=2；In short side chain structure：X=6-10, y=1, z=1, k=0.
6. according to the preparation method described in claim 1, it is characterised in that：B) two kinds of polymerizations in step composite membrane intermediate layer
The content ratio (mass ratio) of resin is, sulfonated polyether-ether-ketone：Perfluorinated sulfonic acid polymer=1:0.6~1:1.2；Resin solution
Mass concentration is 3%~15%；C) in step resin solution mass concentration 3%~15%.
7. according to the preparation method described in claim 1, it is characterised in that：The thickness of intermediate layer (B) is 5~30um.
8. according to the preparation method described in claim 1, it is characterised in that：The thickness of polymeric layer (C) is 5~30um.
9. according to the preparation method described in claim 1, it is characterised in that：The spraying temperature of thermal spraying is 40~80 DEG C.
10. according to the preparation method described in claim 1, it is characterised in that：The composite membrane for preparing need in an oven process 6~
24h, treatment temperature is 70~120 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108428917A (en) * | 2018-01-13 | 2018-08-21 | 素水能源科技（上海）有限公司 | Sulfonated polyimide-Nafion composite membranes and preparation method thereof |
| CN112599824A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Preparation process of composite membrane for fuel cell |
| CN112968199A (en) * | 2019-12-14 | 2021-06-15 | 中国科学院大连化学物理研究所 | Integrated membrane electrode for fuel cell and preparation and application thereof |
| CN114196991A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | Multilayer proton exchange membrane for water electrolysis and preparation method thereof |
| CN114204051A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | Continuous coating preparation process for membrane electrode of fuel cell |
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| US20090169956A1 (en) * | 2007-12-31 | 2009-07-02 | Samsung Electronics Co., Ltd. | Solid proton conductor and fuel cell including the same |
| CN102532575A (en) * | 2010-12-31 | 2012-07-04 | 中国科学院金属研究所 | Preparation method of perfluorinated sulfonic acid resin/sulfonated polyether ether ketone type composite diaphragm |
| CN104733739A (en) * | 2013-12-18 | 2015-06-24 | 上海交通大学 | Inorganic/organic composite proton exchange membrane and production method thereof |
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Patent Citations (3)
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| US20090169956A1 (en) * | 2007-12-31 | 2009-07-02 | Samsung Electronics Co., Ltd. | Solid proton conductor and fuel cell including the same |
| CN102532575A (en) * | 2010-12-31 | 2012-07-04 | 中国科学院金属研究所 | Preparation method of perfluorinated sulfonic acid resin/sulfonated polyether ether ketone type composite diaphragm |
| CN104733739A (en) * | 2013-12-18 | 2015-06-24 | 上海交通大学 | Inorganic/organic composite proton exchange membrane and production method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108428917A (en) * | 2018-01-13 | 2018-08-21 | 素水能源科技（上海）有限公司 | Sulfonated polyimide-Nafion composite membranes and preparation method thereof |
| CN112968199A (en) * | 2019-12-14 | 2021-06-15 | 中国科学院大连化学物理研究所 | Integrated membrane electrode for fuel cell and preparation and application thereof |
| CN112599824A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院大连化学物理研究所 | Preparation process of composite membrane for fuel cell |
| CN112599824B (en) * | 2020-12-14 | 2022-01-28 | 中国科学院大连化学物理研究所 | Preparation process of composite membrane for fuel cell |
| CN114196991A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | Multilayer proton exchange membrane for water electrolysis and preparation method thereof |
| CN114204051A (en) * | 2021-12-03 | 2022-03-18 | 中国科学院大连化学物理研究所 | Continuous coating preparation process for membrane electrode of fuel cell |
| CN114196991B (en) * | 2021-12-03 | 2023-01-06 | 中国科学院大连化学物理研究所 | Multi-layer proton exchange membrane for water electrolysis and preparation method thereof |
| CN114204051B (en) * | 2021-12-03 | 2023-11-10 | 中国科学院大连化学物理研究所 | Continuous coating preparation process for fuel cell membrane electrode |
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